Novel alkylation catalyst and its use in alkylation

ABSTRACT

The invention pertains to a catalyst comprising catalyst particles comprising a hydrogenation function and a solid acid, wherein the ratio between (i) the volume in catalyst pores with a diameter in the range of 40-8000 nm and (ii) the specific length of the catalyst particles is in the range of 0.01-0.90 ml/(g*mm) and wherein the catalyst has a total pore volume of at least 0.20 ml/g and the volume in the catalyst pores with a diameter in the range of 40-8000 nm is below 0.30 ml/g. The invention further pertains to the use of this catalyst in the alkylation of hydrocarbons.

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority from European Application No.00201917, filed May 30, 2000 and from U.S. application Ser. No.60/216,068, filed Jul. 5, 2000.

BACKGROUND OF THE INVENTION

[0002] 1. Field of the Invention

[0003] The present invention relates to a novel alkylation catalyst andthe use thereof for the alkylation of hydrocarbons.

[0004] 2. Description of the Prior Art

[0005] Within the framework of the present invention, the termalkylation refers to the reaction of a hydrocarbon, such as an aromaticor a saturated hydrocarbon, with an olefin. Without limiting the scopeof the invention we will further illustrate the invention by discussingthe alkylation of saturated hydrocarbons, in general branched saturatedhydrocarbons, with an olefin to give highly branched saturatedhydrocarbons with a higher molecular weight. This reaction is ofinterest because it makes it possible to obtain, through the alkylationof isobutane with an olefin containing 2-6 carbon atoms, an alkylatewhich has a high octane number and which boils in the gasoline range.

[0006] Unlike gasoline obtained by cracking heavier petroleum fractionssuch as vacuum gas oil and atmospheric residue, gasoline obtained byalkylation is essentially free of contaminants such as sulfur andnitrogen and so has clean burning characteristics. Its high anti-knockproperties, represented by the high octane number, lessen the need toadd environmentally harmful anti-knock compounds such as lead. Also,unlike gasoline obtained by reforming naphtha or by cracking heavierpetroleum fractions, alkylate contains few if any aromatics or olefins,which, environmentally speaking, is a further advantage.

[0007] The alkylation reaction is acid-catalyzed. At present, incommercial alkylation equipment use is made of liquid acid catalystssuch as sulfuric acid and hydrogen fluoride. The use of such catalystsis attended with a wide range of problems. For instance, sulfuric acidand hydrogen fluoride are highly corrosive, so that the equipment usedhas to meet high quality requirements. Since the presence of highlycorrosive materials in the resulting fuel is objectionable, theremaining acid has to be removed from the alkylate. Also, because of thephase separations, which have to be carried out, the process iscomplicated and thus expensive. Besides, there is always the risk thattoxic substances such as hydrogen fluoride will be emitted.

[0008] A newer development in this field is the use of solid acidcatalysts, such as zeolite-containing catalysts. Thus WO 9823560describes the use of a catalyst containing a zeolite, such as a Yzeolite, and a hydrogenation function, such as a Group VIII noble metal,e.g., platinum or palladium, and, optionally, a matrix material, such asalumina, in the alkylation of saturated hydrocarbons. Though theperformance of this catalyst is satisfactory, there is still a need forfurther increase of catalytic activity, selectivity, and stability ofthese catalysts.

[0009] We have made a surprising discovery that satisfies the above needby choice of catalyst features as set forth in the following discussion.

SUMMARY OF THE INVENTION

[0010] Accordingly, our invention, in one embodiment, comprises acatalyst suitable for use in the alkylation of hydrocarbons whichcomprises catalyst particles comprising a hydrogenation function and asolid acid, wherein the ratio between (i) the volume in catalyst poreswith a diameter in the range of about 40-8000 nm and (ii) the specificlength of the catalyst particles is in the range of about 0.01-0.90ml/(g*mm) and wherein the catalyst has a total pore volume of at leastabout 0.20 ml/g and the volume in the catalyst pores with a diameter inthe range of about 40-8000 nm is below about 0.30 ml/g.

[0011] In a second embodiment our invention comprises a process for theuse of the above catalyst in the alkylation of hydrocarbons,particularly saturated hydrocarbons.

[0012] Other objectives and embodiments of our invention encompassdetails about catalyst compositions and physical structure, detailsconcerning the preparation of the catalyst and the use of the catalystall of which are hereinafter disclosed in the following discussion ofeach of the facets of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

[0013] In the following discussion the pores having a diameter in therange of about 40-8000 nm will be denoted “macropores” and the porevolume in these pores will be designated as “macropore volume”.

[0014] The specific length of the catalyst particle is defined as theratio between the geometric volume and the geometric surface of thesolid part of this catalyst particle. The determination of the geometricvolume and the geometric surface is known to the person skilled in theart and can be carried out, e.g., as described in DE 2354558. It isnoted that the specific length is different from the diameter of thecatalyst particle. E.g., for a cylindrical catalyst particle theparticle diameter is four to six times higher (depending on the diameterand the length of the particle) than the specific length. Further, thediameter of, e.g., a sphere is six times higher than the specificlength.

[0015] As stated above, it is essential to the catalyst of the presentinvention that it has a ratio between macropore volume and specificlength in the range of about 0.01-0.90 ml/(g*mm). As further statedabove, it is essential to the catalyst of the present invention that ithas a total pore volume of at least about 0.20 ml/g and that themacropore volume is below about 0.30 ml/g

[0016] As is shown in the (comparative) examples below, the catalystshows a significantly poorer performance in the alkylation ofhydrocarbon feeds if the ratio between macropore volume and specificlength and/or the total pore volume is outside these ranges.

[0017] Preferably, the ratio between macropore volume and specificlength is above about 0.20 ml/(g*mm), more preferably above about 0.30ml/(g*mm), and even more preferably above about 0.40 ml/(g*mm), as wellas preferably below about 0.80 ml/(g*mm). It is further preferred thatthe catalyst has a total pore volume of at least about 0.23 ml/g andmost preferably of at least about 0.25 ml/g.

[0018] Preferably, the catalyst particles have a specific length of atleast about 0.10 mm, more preferably of at least about 0.16 mm, and mostpreferably of at least about 0.20 mm. The upper limit of the specificlength preferably lies at about 2.0 mm, more preferably at about 1.0 mm,and most preferably at about 0.6 mm.

[0019] The particles of the catalyst of the invention can have manydifferent shapes, including spheres, cylinders, rings, and symmetric orasymmetric polylobes, for instance tri- and quadrulobes. Preferably, thecatalyst particles have an average particle diameter of at least about0.5 mm, more preferably of at least about 0.8 mm, and most preferably ofat least about 1.0 mm. The upper limit of the average particle diameterpreferably lies at about 10.0 mm, more preferably at about 5.0 mm, evenmore preferably at about 3.0 mm.

[0020] Preferably, the macropore volume ranges from about 0.05 to about0.30 ml/g, more preferably from about 0.08 to about 0.30 ml/g, and evenmore preferably from about 0.08 to about 0.25 ml/g.

[0021] The catalyst comprises a solid acid, such as a zeolite. Examplesof zeolites contained in the catalyst of the invention are Y-zeolites,including H-Y-zeolites and USY-zeolites, zeolite beta, MCM-22, andMCM-36. Preferably, the zeolite is Y-zeolite with a unit cell size inthe range of about 24.34-24.72 angstroms. More preferably, the zeoliteis a Y-zeolite with a unit cell size in the range of about 24.40-24.61angstroms and a silica:alumina molar ratio in the range about 7-18 andmost preferably the zeolite is a Y-zeolite with a unit cell size in therange of about 24.24-24.58 angstroms and a silica:alumina molar ratio inthe range about 7.85-13.75.

[0022] As stated above, the catalyst comprises a hydrogenation function.A suitable hydrogenation function, e.g., comprises a Group VIII noblemetal. The Group VIII noble metal preferably is contained in thecatalyst in an amount of about 0.01-2 wt %, and more preferably about0.1-1 wt %, calculated as metal and based on the weight of the solidacid. Preferably, the Group VIII noble metal comprises palladium and/orplatinum.

[0023] Preferably, the catalyst additionally comprises a matrixmaterial. Examples of suitable matrix materials are alumina, silica,titania, zirconia, clays, and mixtures thereof. Matrix materialscomprising alumina are generally preferred.

[0024] Preferably, the catalyst of the invention comprises about 2-98 wt% of the solid acid and about 98-2 wt % of the matrix material, based onthe total weight of the solid acid and matrix material present in thecatalyst. More preferably, the catalyst comprises about 10-90 wt % ofthe solid acid and about 90-10 wt % of the matrix material, based on thetotal weight of the solid acid and matrix material contained in thecatalyst. Even more preferably, the catalyst comprises about 20-80 wt %of the solid acid and about 80-20 wt % of the matrix material, mostpreferably about 50-80 wt % of the solid acid and about 20-50 wt % ofthe matrix material, based on the total weight of the solid acid andmatrix material contained in the catalyst.

[0025] If desired, the solid acid can also comprise non-zeolitic solidacids such as silica-alumina, sulfated oxides, such as sulfated oxidesof zirconium, titanium, or tin, mixed oxides of zirconium, molybdenum,tungsten, phosphorus, etc., chlorinated aluminum oxides or clays.

[0026] Preferably, the catalyst consists essentially of a hydrogenationfunction, a solid acid, and, optionally, a matrix material. Morepreferably, the catalyst consists essentially of a zeolite, a Group VIIInoble metal, and a matrix material. It is further preferred that thecatalyst is essentially free of rare earth metals and/or Group VIIInon-noble metals. Thus, most preferably, the catalyst of the inventionconsists essentially of a Group VIII noble metal compound, a zeolite,and a matrix, wherein

[0027] (i) the zeolite consists essentially of oxidic compounds (oxidesand hydroxides) of a Group III element, such as aluminum, and/or of aGroup IV element, such as silicon, and, optionally, oxidic compounds ofa Group I element, such as sodium, and/or of a Group II element, such ascalcium, and/or of a Group V element, such as phosphorus, and,optionally, additionally ammonium and/or water, and

[0028] (ii) the matrix is selected from the group of oxidic compounds ofsilicon, aluminum, titanium, zirconium, Group II metals or mixturesthereof.

[0029] The catalyst can be prepared by processes common to the industry.A typical process comprises the successive steps of

[0030] (i) shaping, e.g., extruding the solid acid constituent,optionally after mixing it with a matrix material, to form particles,

[0031] (ii) calcining the resulting particles, and

[0032] (iii) incorporating the hydrogenation function into the calcinedparticles by, e.g., impregnating the particles with a solution of ahydrogenation metal component and/or by (competitive) ion exchange.

[0033] Alternatively, the catalyst can, e.g., be prepared by a processcomprising the successive steps of

[0034] (i) incorporating the hydrogenation function into the solid acidconstituent or into a mixture of the solid acid constituent and thematrix material,

[0035] (ii) shaping, e.g., extruding the resulting material to formparticles, and

[0036] (iii) calcining the resulting particles.

[0037] The catalyst is particularly suitable for the alkylation ofsaturated hydrocarbons. The invention therefore further pertains to theuse of the catalyst of the invention in the alkylation of thesefeedstocks. As stated above, this comprises the reaction of a saturatedhydrocarbon with an olefin or olefin precursor in the presence of thecatalyst of the invention to give highly branched saturated hydrocarbonswith a higher molecular weight.

[0038] Preferably, the hydrocarbon is a branched saturated hydrocarbonsuch as an isoalkane having about 4-10 carbon atoms. Examples areisobutane, isopentane, isohexane or mixtures thereof, with isobutanebeing most preferred. The olefins to be used in the alkylation processgenerally have about 2-10 carbon atoms, preferably 2-6 carbon atoms,still more preferably about 3-5 carbon atoms, and most preferably about4 carbon atoms. Most preferably, the alkylation process consists of thealkylation of isobutane with butenes.

[0039] As will be evident to the skilled person, the alkylation processcan be applied in any suitable form, including fluidized bed processes,slurry processes, and fixed bed processes. The process may be carriedout in a number of beds and/or reactors, each with separate olefinaddition. In such a case, the process of the invention may be carriedout in each separate bed or reactor.

[0040] Suitable process conditions are known to the skilled person.Preferably, an alkylation process as disclosed in WO 9823560 is applied.The process conditions applied in this process are summarized in thefollowing Table: Temperature pressure range molar ratio of saturatedrange [° C.] [bar] hydrocarbon to olefin preferred −40-250   1-100 5:1-5000:1 more preferred  0-150 10-40 50:1-1000:1 most preferred60-95  15-30 150:1-750:1 

[0041] Preferably, a regeneration technique as described in WO 9823560is applied during the alkylation process. More in particular, during thealkylation process the catalyst is preferably subjected intermittentlyto a regeneration step by being contacted with a feed containing analiphatic compound and hydrogen, with said regeneration preferably beingcarried out at about 90% or less, more preferably at about 60% or less,even more preferably at about 20% or less, and most preferably at about10% or less of the active cycle of the catalyst. The active cycle of thecatalyst is defined as the time from the start of the feeding of thealkylation agent to the moment when, in comparison with the entrance ofthe catalyst-containing reactor section, about 20% of the alkylationagent leaves the catalyst-containing reactor section without beingconverted, not counting isomerisation inside the molecule.

[0042] Optionally, in this process, the catalyst can be subjectedperiodically to a high-temperature regeneration with hydrogen in the gasphase. This high-temperature regeneration is preferably carried out at atemperature of at least about 150° C., more preferably at about175°-600° C., and most preferably at about 200°-400° C. For details ofthis regeneration procedure, reference is made to WO 9823560, and inparticular to page 4, lines 5-19 and page 9, line 13 through page 13,line 2.

[0043] The use of the catalyst of the present invention in the abovealkylation process results in a high olefin conversion (amount of olefinin the feed that is converted in the reaction), a high C5+ alkylateyield (weight amount of C5+ alkylate produced divided by the overallweight of olefin consumed) and a high octane number, while the amount ofundesired C9+ by-products can be restricted and the catalyst's stabilitycan thus be improved. For details in respect of these parameters,reference is made to WO 9823560.

[0044] The following characterization method was applied in the presentinvention: The macropore volume as well as the total pore volume weredetermined via mercury intrusion on the basis of the Washburn equation$D = \frac{{- 4}\gamma \quad \cos \quad \theta}{p}$

[0045] with D being the pore diameter, p being the pressure appliedduring the measurement, y being the surface tension, taken to be 480dynes/cm, and θ being the contact angle, taken to be 140° In the presentmeasurement, the pressure was varied over such a range that themeasurement covered pores with a diameter in the range of 3.6-8000 nm.

[0046] The present invention will be further illustrated by way of thefollowing examples:

[0047] General test procedure

[0048] A fixed-bed recycle reactor as described in WO 9823560 having adiameter of 2 cm was filled with a 1:1 volume/volume mixture of 38.6grams of catalyst extrudates and carborundum particles (60 mesh). At thecenter of the reactor tube a thermocouple of 6 mm in diameter wasarranged. The reactor was flushed with nitrogen for 30 minutes (100Nl/hour). Next, the system was tested for leakages at elevated pressure,after which the pressure was raised to 21 bar and the nitrogen replacedby hydrogen (100 Nl/hour). The reactor temperature was then raised to200° C. at a rate of 1° C./min. After 1 hour at 200° C. the temperaturewas raised to 400° C. at a rate of 1° C./min. After 1 hour at 400° C.the reactor temperature was lowered to the reaction temperature, whichis given in the Examples below.

[0049] The hydrogen stream was stopped with the attaining of thereaction temperature. Isobutane was supplied to the reactor at a rate ofabout 4,000 grams/hour. About 95-98% of the isobutane was fed back tothe reactor. About 2-5% was drained off for analysis. Such an amount ofisobutane was supplied to the reactor to ensure a constant quantity ofliquid in the system. When the system had stabilized, such an amount ofcis-2-butene was added to it as to give a cis-2-butene-WHSV as given inthe examples below (calculated on zeolite weight in the catalystsample). The overall rate of flow of liquid in the system was maintainedat about 4,000 g/h. The weight ratio of isobutane to cis-2-butene in thereactor supply (without considering the unreacted material fed back tothe reactor) is given in the Examples below. The pressure in the reactoramounted to 21 bar.

[0050] Each time after 1 hour of reaction, the catalyst was regeneratedby being washed with isobutane for 5 minutes, followed by 50 minutes ofregeneration through being contacted with a solution of 1 mol % of H2 inisobutane, and then being washed with isobutane for another 5 minutes(total washing and regeneration time 1 hour). After this washing step,alkylation was started again. The process conditions during the washingsteps and the regeneration step were the same as the process conditionsduring the reaction step.

[0051] Unless specified otherwise, the catalytic performance wasmeasured after a steady state was reached. The performance wascharacterized by the olefin conversion, the research octane number(RON), the C5+ alkylate yield, and the weight percentage of undesiredC9+ by-products (excl. 2,2,5-trimethylhexane), calculated on C5+alkylate. The RON was determined as described on pages 13 and 14 of WO9823560, the only exception being that the RON contribution of total C9+(excl. 2,2,5-trimethylhexane) was estimated to be 84 instead of 90. TheC5+alkylate yield is defined as the weight amount of C5+ alkylateproduced divided by the overall weight of olefin consumed.

EXAMPLE 1

[0052] A catalyst of the invention was tested according to theabove-described test procedure. The weight ratio of isobutane tocis-2-butene in the reactor supply (without considering the unreactedmaterial fed back to the reactor) was 20. The reaction temperature was70° C. The cis-2-butene-WHSV was 0.21 h-1. The catalyst had thefollowing properties: Catalyst composition: Solid acid: USY-zeoliteSolid acid amount: 70 wt % (based on the total weight of solid acid andmatrix) Hydrogenation metal: platinum Hydrogenation metal amount: 0.34wt % Matrix: alumina Matrix amount: 30 wt % (based on the total weightof solid acid and matrix) Catalyst shape: cylindrical extrudatesPore/particle characteristics: Macropore volume: 0.17 ml/g Specificlength: 0.22 mm (average diameter: 1.0 mm, average length: 4 mm)Macropore volume/ 0.77 ml/(g*mm) specific length Total pore volume: 0.36ml/g

[0053] The catalytic performance is given in the Table below.

EXAMPLE 2

[0054] A catalyst with the same composition and shape as the catalyst ofExample 1 was tested. The catalyst had a ratio between macropore volumeand specific length of 0.64 ml/(g*mm) (macropore volume: 0.14 ml/g,specific length: 0.22 mm (average diameter: 1.0 mm, average length: 4mm)). Its total pore volume was 0.35 ml/g. The weight ratio of isobutaneto cis-2-butene in the reactor supply (without considering the unreactedmaterial fed back to the reactor) was 19. The reaction temperature was70° C. The cis-2-butene-WHSV was 0.21 h-1. The further test conditionswere as described in Example 1. The catalytic performance is given inthe Table below.

EXAMPLE 3

[0055] A catalyst with the same composition and shape as the catalyst ofExample 1 was tested. It had a ratio between macropore volume andspecific length of 0.41 ml/(g*mm) (macropore volume: 0.09 ml/g, specificlength: 0.22 mm (average diameter: 1.0 mm, average length: 4 mm)). Itstotal pore volume was 0.27 ml/g. The weight ratio of isobutane tocis-2-butene in the reactor supply (without considering the unreactedmaterial fed back to the reactor) was 19. The reaction temperature was70° C. The cis-2-butene-WHSV was 0.21 h-1. The further test conditionswere as described in Example 1. The catalytic performance is given inthe Table below.

EXAMPLE 4

[0056] A catalyst with the same composition and shape as that of Example1 was tested. It had a ratio between macropore volume and specificlength of 0.49 ml/(g*mm) (macropore volume: 0.17 ml/g, specific length:0.35 mm (average diameter: 1.7 mm, average length: 4 mm)). Its totalpore volume was 0.38 ml/g. The weight ratio of isobutane to cis-2-butenein the reactor supply (without considering the unreacted material fedback to the reactor) was 26. The reaction temperature was 80° C. Thecis-2-butene-WHSV was 0.19 h-1. The further test conditions were asdescribed in Example 1. The catalytic performance is given in the Tablebelow.

COMPARATIVE EXAMPLE A

[0057] A catalyst with the same composition and shape as the catalyst ofExample 1 was tested. It had a ratio between macropore volume andspecific length of 0.95 ml/(g*mm) (macropore volume: 0.21 ml/g, specificlength: 0.22 mm (average diameter: 1.0 mm, average length: 4 mm)), whichlies outside the claimed range. Its total pore volume was 0.50 ml/g. Theweight ratio of isobutane to cis-2-butene in the reactor supply (withoutconsidering the unreacted material fed back to the reactor) was 30. Thereaction temperature was 70° C. The cis-2-butene-WHSV was 0.21 h-1. Thefurther test conditions were as described in Example 1. The catalyticperformance is given in the Table below.

COMPARATIVE EXAMPLE B

[0058] A catalyst with the same composition and shape as the catalyst ofExample 1 was tested. It had a ratio between macropore volume andspecific length of 0.18 ml/(g*mm) (macropore volume: 0.04 ml/g, specificlength: 0.22 mm (average diameter: 1.0 mm, average length: 4 mm)). Itstotal pore volume was 0.19 ml/g, which lies outside the claimed range.The weight ratio of isobutane to cis-2-butene in the reactor supply(without considering the unreacted material fed back to the reactor) was27. The reaction temperature was 80° C. The cis-2-butene-WHSV was 0.19h-1. The further test conditions were as described in Example 1. As asteady state could not be reached, the catalytic performance wasmeasured after 60 hours. The results are given in the Table below.

[0059] Discussion:

[0060] The catalytic performance of the catalysts of the above Examplesis summarized in the Table below: Com. Com. Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex.A Ex. B Total pore 0.36 0.35 0.27 0.38 0.50 0.19 volume [ml/g] Macropore0.77 0.64 0.41 0.49 0.95 0.18 volume/specific length [ml/(g*mm)] Olefin100 99.9 100 99.7 99.5 98.4 conversion [%] wt % C9+ 5.3 6.4 5.0 6.1 1310 (excl. 2,2,5- trimethyl- hexane), calc. on C5+ alkylate RON (research95.7 96.0 96.1 95.7 95.6 95.0 octane number) C5+ alkylate 205 207 206202 185 183 yield [%]

[0061] The performance of the catalysts of Comparative Examples A and Bis significantly worse than that in Examples 1-4. More in particular,the C5+ alkylate yield is significantly lower than the correspondingyields of the catalysts according to the invention, whereas the weightpercentage of undesired C9+ lies significantly above the correspondingvalues of the catalysts of Examples 1-4.

[0062] It is noted that this poor performance of the catalysts ofComparative Examples A and B is observed despite the fact that they weretested at conditions that should lead to a better catalytic performancethan the conditions under which the catalysts of Examples 1-4 weretested. More in particular, the weight ratio between isobutane andcis-2-butene in Comparative Examples A and B is higher than in Examples1-4. A higher weight ratio implies a lower amount of olefin in thereactor and thus a lower risk of excess olefin being able to react withthe formed alkylate resulting in undesired C9+ products.

We claim:
 1. A catalyst suitable for use in the alkylation ofhydrocarbons which comprises catalyst particles comprising ahydrogenation function and a solid acid, wherein the ratio between (i)the volume in catalyst pores with a diameter in the range of about40-8000 nm and (ii) the specific length of the catalyst particles is inthe range of about 0.01-0.90 ml/(g*mm) and wherein the catalyst has atotal pore volume of at least about 0.20 ml/g and the volume in thecatalyst pores with a diameter in the range of about 40-8000 nm is belowabout 0.30 ml/g.
 2. The catalyst of claim 1 wherein the ratio between(i) the volume in catalyst pores with a diameter in the range of about40-8000 nm and (ii) the specific length of the catalyst particles is atleast about 0.20 ml/(g*mm).
 3. The catalyst of claim 1 wherein thecatalyst has a total pore volume of at least about 0.23 ml/g.
 4. Thecatalyst of claim 1 wherein the hydrogenation function consistsessentially of a Group VIII noble metal.
 5. The catalyst of claim 1wherein the solid acid is a Y-zeolite with a unit cell size in the rangeof about 24.34-24.72 angstroms.
 6. The catalyst of claim 5 wherein thesolid acid is a Y zeolite with a unit cell size in the range of about24.40-24.61 angstroms.
 7. The catalyst of claim 6 wherein the solid acidis a Y zeolite with a unit cell size in the range of about 24.45-24.58angstroms.
 8. The catalyst of claim 1 wherein the catalyst additionallycomprises a matrix material.
 9. The catalyst of claim 8 wherein thematrix material comprises alumina.
 10. The catalyst of claim 1 whereinthe catalyst is free of rare earth metals and Group VIII non-noblemetals.
 11. A process for the alkylation of hydrocarbons wherein ahydrocarbon feedstock and an olefin are contacted with the catalyst ofclaim 1 at alkylation process conditions.
 12. A process for thealkylation of saturated hydrocarbons wherein a saturated hydrocarbonfeedstock and an olefin are contacted with the catalyst of claim 1 atalkylation process conditions.